PEO-based polymer electrolytes

Like a liquid solvent, poly(ethylene oxide) dissolves a wide variety of inorganic salts. Ionic conductivity occurs in the amorphous region of the polymer and typically both anions and cations are mobile to some extent. This paper discusses the preparation, thermal behaviour and ionic transport of thin cast films of PEO-based electrolytes containing monovalent and divalent cations. The techniques that shed light on the structure-conductivity relationship are emphasized. The temperature and composition dependence of conductivity is also considered. Finally, attention has been paid to the possible uses of these polymeric electrolytes in solid-state electrochemical devices such as primary and secondary batteries, electrochromic displays and sensors.     

Effect of ethylene carbonate on properties of PVP-CsAlO2-LiClO4 solid polymer electrolytes

ABSTRACT

Solid polymer electrolytes (SPEs) have been widely studied due to its extensive applications in high energy rechargeable batteries, supercapacitors, fuel cells, photoelectrochemical and electrochromic displays. Herein, SPEs based on polyvinyl pyrrolidone (PVP) doped with cesium aluminate (CsAlO₂) nanoparticles (NPs), lithium perchlorate (LiClO₄) as an electrolyte and varying amounts viz., 2, 4, 6 and 8 wt.% of ethylene carbonate (EC) as plasticizer have been fabricated by solution intercalation technique. The structural features of PVP-CsAlO₂-LiClO₄-EC SPEs have been studied by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The morphology of PVP-CsAlO₂-LiClO₄-EC SPEs has been examined by scanning electron microscopy (SEM). The thermal properties of the SPEs were characterized by the thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) techniques. The TGA and DSC results revealed that a significant reduction in thermal stability and glass transition temperature (T_g) of PVP with an increase in EC content in SPE films. The optoelectrical properties of PVP-CsAlO₂-LiClO₄-EC SPE films have been evaluated using UV–visible spectroscopy. The band gap energy (E_g) was found to decrease with an increase in EC content, exhibiting a minimum of 4.23 eV for PVP-8 wt.% CsAlO₂-15 wt.% LiClO₄-8 wt.% EC. This could be ascribed to the formation of localized states and increased degree of disorder in the PVP-CsAlO₂-LiClO₄ SPE films. The integrated plasticizers increase the values of refractive index (RI), optical conductivity, and dielectric constants of PVP-CsAlO₂-LiClO₄ SPE films. The AC conductivity of the SPEs has been evaluated at room temperature using digital LCR meter in the frequency range 100 Hz – 5 MHz. The conductivity strongly depends on CsAlO₂ NPs and EC plasticizer content in SPEs.     

Ionic conductivity of a novel solid polymer electrolyte

A novel kind of solid polymer electrolyte, the solvation unit of which is O?CNHR, has been studied. The effects of host polymer structure, ion species, salt concentration, and plasticizers on ionic conductivity are discussed in detail. The solvability of host polymers is a very important factor that affects the ionic conductivity of electrolytes and is fully decided by the structure of solvation units and their density in polymer chain. The latter two rest with monomers structure and copolymerization ratio. Effects of alkali metal salts and divalent metal salts on ionic conductivity are different because of their different leading factor of cation radius. Salt concentration dependence of ionic conductivity appears as a double‐peak shape when alkali metal salts are added because of the total contribution of two kinds of ionic conductance modes, and appears as similar shapes when divalent metal salts are added. Different influences of plasticizers on ionic conductivity result from their different action ways. Ethylene glycol acts well because of its effective action from three different modes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2176–2184, 2001     

Ionic conductivity of solid polymer electrolytes for dye‐sensitized solar cells

We developed an ionic conductivity model of solid polymer electrolytes for dye‐sensitized solar cells (DSSCs) based on the Nernst–Einstein equation in which the diffusion coefficient is derived from the molecular thermodynamic model. We introduced concentration‐dependence of the diffusion coefficient into the model, and the diffusion coefficient was expressed by differentiating the chemical potential by concentration. The ionic conductivities of polymer electrolytes (PEO/LiI/I₂ system) were investigated at various temperatures and compositions. We prepared a set of PEO in which an EO : LiI mole ratio of 10 : 1 was kept constant for PEO·LiI·(I₂)_n compositions with n = 0.02, 0.05, 0.1, 0.15, 0.2, and 0.3 (mole ratio of LiI : I₂). The ionic conductivities of the electrolytes were measured using a stainless steel/polymer‐electrolyte/stainless steel sandwich‐type electrode structure using alternating current impedance analysis. The values calculated using the proposed model agree well with experimental data. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Conductivity studies of solid polymer electrolytes based on polyethers and polyphosphazene blends

In this work, electrical characteristics of several polymer electrolytes based on polyether and polyphosphazene blends are reported by means of complex impedance spectroscopy. In addition, a statistical analysis was conducted applying a mathematical model to a previously designed pattern to the purpose of gaining insight into the effect exerted on the conductivity of the electrolyte by the portion of each component in the blend. Evidence was obtained to prove that the dependence of conductivity on blend composition adjusts to a reduced cubic model, whose regression coefficients are determined in this work. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2181–2186, 1998     

Composite polymer electrolytes based on the low crosslinked copolymer of linear and hyperbranched polyurethanes

Low crosslinked copolymer of linear and hyperbranched polyurethane (CHPU) was prepared, and the ionic conductivities and thermal properties of the composite polymer electrolytes composed of CHPU and LiClO₄ were investigated. The FTIR and Raman spectra analysis indicated that the polyurethane copolymer could dissolve more lithium salt than the corresponding polymer electrolytes of the non crosslinked hyperbranched polyurethane, and showed higher conductivities. At salt concentration EO/Li = 4, the electrolyte CHPU30‐LiClO₄ reached its maximum conductivity, 1.51 × 10^?5 S cm^?1 at 25°C. DSC measurement was also used for the analysis of the thermal properties of polymer electrolytes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3607–3613, 2007     

Preparation and characterization of novel hybrid thermoplastic poly(ether urethane)/poly(vinylidene fluoride) elastomers,and their application as solid polymer electrolytes

A comb‐like polyether, poly(3‐2‐[2‐(2‐methoxyethoxy)ethoxy]ethoxymethyl‐3′‐methyloxetane) (PMEOX), was reacted with hexamethylene diisocyanate and extended with butanediol in a one‐pot procedure to give novel thermoplastic elastomeric poly(ether urethane)s (TPEUs). The corresponding hybrid solid polymer electrolytes were fabricated through doping a mixture of TPEU and poly(vinylidene fluoride) with three kinds of lithium salts, LiClO₄, LiBF₄ and lithium trifluoromethanesulfonimide (LiTFSI), and were characterized using differential scanning calorimetry, thermogravimetric analysis and Fourier transform infrared spectroscopy. The ionic conductivity of the resulting polymer electrolytes was then assessed by means of AC impedance measurements, which reached 2.1 × 10^?4 S cm^?1 at 30 °C and 1.7 × 10^?3 S cm^?1 at 80 °C when LiTFSI was added at a ratio of O:Li = 20. These values can be further increased to 3.5 × 10^?4 S cm^?1 at 30 °C and 2.2 × 10^?3 S cm^?1 at 80 °C by introducing nanosized SiO₂ particles into the polymer electrolytes. Copyright © 2006 Society of Chemical Industry     

Ionic conductivity and physical stability study of gel nework polymer electrolytes

Gel polymer electrolytes (GPE) were prepared by a crosslinking reaction between poly(ethylene glycol) and a crosslinking agent with three isocyanate groups in the presence of propylene carbonate (PC) and ethylene carbonate (EC) or their mixture, and their ionic conducting behavior was carefully investigated. When the plasticizer amount was fixed, the ionic conductivity was greatly influenced by the nature of plasticizers. It was found that the conductivity data followed the Arrhenius equation in the GPE. Whatever plasticizer was used, a maximum ambient conductivity was found at a salt concentration near [Li⁺]/[EO] equal to 0.20. The physical stability of GPE was studied qualitatively by weight loss of GPE under pressure. It was shown that the stability was greatly affected by the network structure of the GPE and the most stable one in our research was the GPE containing the PEO₁₀₀₀ segment, which has a strong interaction between network and plasticizers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2957–2962, 2000     

Effect of surface modified porous inorganic-organic hybrid polyphosphazene nanotubes on the properties of polyethylene oxide based solid polymer electrolytes

2-(2-methyloxyethoxy)ethanol modified poly (cyclotriphosphazene-co-4,4′-sufonyldiphenol) (PZS) nanotubes were synthesized and solid composite polymer electrolytes based on the surface modified polyphosphazene nanotubes added to PEO/LiClO₄ model system were prepared. Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) were used to investigate the characteristics of the composite polymer electrolytes (CPE). The ionic conductivity, lithium ion transference number and electrochemical stability window can be enhanced after the addition of surface modified PZS nanotubes. The electrochemical investigation shows that the solid composite polymer electrolytes incorporated with PZS nanotubes have higher ionic conductivity and lithium ion transference number than the filler SiO₂. Maximum ionic conductivity values of 4.95 × 10⁻⁵ S cm⁻¹ at ambient temperature and 1.64 × 10⁻³ S cm⁻¹ at 80 °C with 10 wt % content of surface modified PZS nanotubes were obtained and the lithium ion transference number was 0.41. The good chemical properties of the solid state composite polymer electrolytes suggested that the inorganic-organic hybrid polyphosphazene nanotubes had a promising use as fillers in solid composite polymer electrolytes and the PEO₁₀-LiClO₄-PZS nanotubes solid composite polymer electrolyte can be used as a candidate material for lithium polymer batteries.     

聚合物及离子液体电解质在锂二次电池中的应用

系统地介绍了锂离子二次电池电解质,特别是聚合物电解质及离子液体电解质的应用研究现状。开发具有高能量密度、稳定的充放电性能、循环寿命长、可塑性、高安全性与低成本的锂离子电池是当前的研究热点。离子液体具有较高的离子电导率、宽电化窗口,且无蒸汽压,而聚合物具有良好的机械加工性能。二者的结合将为锂离子电池电解质的研究提供了新的开发思路。     

Structural characterization of new poly(ethylene oxide)-based alkaline solid polymer electrolytes

A new class of alkaline solid polymer electrolytes (SPEs) based on poly(ethylene oxide) (PEO), potassium hydroxide (KOH), and water was investigated. The structure of the SPEs was studied by differential scanning calorimetry, thermogravimetric analysis (TGA), X-ray diffraction, and optical microscopy techniques. The existence of a crystalline complex between PEO, KOH, and H₂O was evidenced for some compositions, depending on the O/K ratio. A possible structure was proposed, and a schematic phase diagram was established for this PEO–KOH–H₂O system. The first conductivity measurements also revealed the great interest of these systems, with conductivity values up to 10^-3 S/cm. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:601–607, 1997     

Preparation and ionic conductivity of solid polymer electrolyte based on polyacrylonitrile‐polyethylene oxide

The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO₄ complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10^?4 S/cm with an [Li⁺]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006     

Overview and perspectives of solid electrolytes for sodium batteries

Quoting the abundance and cost of sodium reserve and robustly safe and high-energy solid electrolytes, sodium solid-state batteries (SSBs) exhibit huge promise for future energy storage applications compared to battery systems using organic liquid electrolytes and Li counterparts. However, the progress and application are still in infancy, experiencing numerous challenges for sodium SSBs due to inherent properties, interface complications, and fabrication. These are recently receiving unprecedented research attention by understanding and steadily resolving the issues associated with sodium SSBs. In this review, the governing bulk and interfacial issues and dynamics, background research correlations from Li counterparts, and strategies to address them are investigated for various ceramic-, polymer-, and ceramic–polymer composite based solid electrolytes. Particular attention is devoted to issues with ceramic electrolytes (such as interfacial stability, brittleness, porosity, and grain–grain boundary resistance) and polymer electrolytes (like dendrite formation, passivation layer, electrochemical instability, and ionic conductivity), and finally, robustness in overall performance and a few drawbacks (such as filler agglomeration, interface dynamics, and crack propagation) on the composited state-of-the-art ceramic–polymer electrolytes are highlighted. To end with, crucial inferences and future research perspectives are condensed on the development of enhanced solid electrolytes for sodium SSBs overcoming the shortcomings illustrated for different electrolytes.     

The effect of ionic liquid fragment on the performance of polymer electrolytes

An ionic liquid 1‐methyl‐3‐[2‐(methacryloyloxy)ethyl]imidazolium bis(trifluoromethane sulfonylimide) (MMEIm‐TFSI) was synthesized and polymerized. Composite polymer electrolytes based on polymeric MMEIm‐TFSI (PMMEIm‐TFSI) and poly[(methyl methacrylate)‐co‐(vinyl acetate)] (P(MMA‐VAc)) were prepared, with lithium bis(trifluoromethane sulfonylimide) (LiTFSI) as target ions (Li⁺). DSC/TGA analysis showed good flexibility and thermal stability of the composite electrolyte membranes. The AC impedance showed that the ionic conductivity of the electrolytes increased with PMMEIm‐TFSI up to a maximum value of 1.78 × 10^?4 S cm^?1 when the composition was 25 wt% P(MMA‐VAc)/75 wt% PMMEIm‐TFSI/30 wt% LiTFSI at 30 °C. The composite electrolyte membrane (transmittance ≥ 90%) can also be used as the ion‐conductive layer material for electrochromic devices, and revealed excellent colorization performance. Copyright © 2011 Society of Chemical Industry     

Electroplasticity memory devices using conducting polymers and solid polymer electrolytes

Erasable memory devices are fabricated by the combination of a conducting polymer and solid polymer electrolyte. The former is used as a memory channel and the latter as an electrolyte medium. The channel conductivity can be controlled over 3-4 orders of magnitude by electrochemical doping through a writing electrode. The response time, depending on the writing voltage, is several seconds. The characteristics of the memory device are discussed.     

Solid polymer electrolytes with stable electrochemical properties

In order to build solid-state ambient-temperature batteries with stable electrochemical performances over a period of months, the crystallization process in polymer electrolytes can be suppressed by the addition of an elastomer and a styrenic macromonomer of PEO to a PEO-lithium salt electrolyte. Complex impedance measurements and X-ray diffraction studies were carried out in an attempt to understand the effect of the macromonomer on the electrochemical behaviour. The conductivity was found to increase with macromonomer content and values as high as 10^?5S cm^?1 at room temperature can be obtained. X-ray, diffraction patterns have shown that addition of the elastomer and the macromonomer does not alter the monoclinic unit cell of the crystallized PEO. During ageing, the diffraction lines were found not to vary appreciably over a period of 15 months. Similarly, no appreciable change in the conductivity level was noticed within the same period. The observed behaviour was explained as a suppression of the crystallization process.     

Dislocation-tuned electrical conductivity in solid electrolytes (9YSZ): A micro-mechanical approach

Tailoring the electrical conductivity of functional ceramics by introducing dislocations is a comparatively recent research focus, and its merits were demonstrated through mechanical means. Especially bulk deformation at high temperatures is suggested to be a promising method to introduce a high dislocation density. So far, however, controlling dislocation generation and their annihilation remains difficult. Although deforming ceramics generate dislocations on multiple length scales, dislocation annihilation at the same time appears to be the bottleneck to use the full potential of dislocations-tailoring the electrical conductivity. Here, we demonstrate the control over these aspects using a micromechanical approach on yttria-stabilized zirconia - YSZ. Targeted indentation well below the dislocation annihilation temperature resulted in extremely dense dislocation networks, visualized by chemical etching and electron channeling contrast imaging. Microcontact-impedance measurements helped evaluate the electrical response of operating individual slip systems. A significant conductivity enhancement is revealed in dislocation-rich regions compared to pristine ones in fully stabilized YSZ. This enhancement is mainly attributed to oxygen ionic conductivity. Thus, the possibility of increasing the conductivity is illustrated and provides a prospect to transfer the merits of dislocation-tuned electrical conductivity to solid oxygen electrolytes.     

Effect of a novel amphipathic ionic liquid on lithium deposition in gel polymer electrolytes

A novel dimeric ionic liquid based on imidazolium cation and bis(trifluoromethanesulfonyl) imide (TFSI) anion has been synthesized through a metathesis reaction. Its chemical shift values and thermal properties are identified via ¹H nuclear magnetic resonance (NMR) imaging and differential scanning calorimetry (DSC). The effect of the synthesized dimeric ionic liquid on the interfacial resistance of gel polymer electrolytes is described. Differences in the SEM images of lithium electrodes after lithium deposition with and without the 1,1′-pentyl-bis(2,3-dimethylimidazolium) bis(trifluoromethane-sulfonyl)imide (PDMITFSI) ionic liquid in gel polymer electrolytes are clearly discernible. This occurs because the PDMITFSI ionic liquid with hydrophobic moieties and polar groups modulates lithium deposit pathways onto the lithium metal anode. Moreover, high anodic stability for a gel polymer electrolyte with the PDMITFSI ionic liquid was clearly observed.     

Preparation of solid-state composite electrolytes based on organic/inorganic hybrid star-shaped polymer and PEG-functionalized POSS for all-solid-state lithium battery applications

A series of composite electrolytes (CEs) consisting of organic/inorganic hybrid star-shaped polymer (SPP13), plasticizer (PEG-functionalized POSS derivatives), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared to investigate the effects of the composite compositions and PEG chain length of PEs on the properties of CEs. SPP13 was prepared via ATRP from poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryl-cyclohexyl-POSS (MA-POSS) using an octafunctional initiator, and the PEG-functionalized POSS derivatives were synthesized by the hydrosilylation reaction of octakis(dimethylsilyloxy)silsesquioxane (OHPS) and allyl-PEG. The CEs were found to be dimensionally-stable enough to separate the electrodes in batteries, but they still possessed high mobility of ion-conducting P(PEGMA) segments, as estimated by the low glass transition temperatures (T_g). The CEs having solid-state show quite high ionic conductivity (4.5 × 10⁻⁵ S cm⁻¹ at 30 °C) which is about three times of magnitude larger than that of the matrix polymer (SPP13) electrolyte (1.5 × 10⁻⁵ S cm⁻¹ at 30 °C). The CEs were electrochemically stable up to +4.2 V without the decomposition of electrolytes. An all-solid-state lithium battery prepared from the CEs exhibited larger discharge capacity than that prepared from the SPP13 electrolyte at 60 °C.